Vat dye and process of producing the same



" -blue tint, buttheir fa-stness to Patented Oct. 8 1929 UNITED. STATES BERG,

PATENT OFFICE UNUS, RUDOLF BRUNE, 0F HOCHST-ON-THE- AND ER-WIN HOFFA, FRITZ MT TLLERQ GERMANY, ASSIGNORS TO GENERAL CORPORATION OF DELAWARE VAT DYE AND PROCESS OF PRODUCING- THE SAME No Drawing. Application filed May 3, 1926, Serial No. 106,492, and in Germany May 6, 1925.

The present invention relates to the new vat'dyestufi's of the general formula:

The manufacture of the 4-1nethyl-5.6-dir halogen-hydroxy-thionaphthene is described in U. s. P. 1,610,539.

Instead of using as starting material a 4 methyl-5.6 dihalogenhydroxythionaphthene,

there may also be used as such. a 3-methyl-t5- dihalogen-1-tl1ioglycollic-2-carb0xylic acid,

provided that the latter is transformed by the existing conditions of the reaction into the corresponding hydroxythionaphthene or a reactive derivative thereof The properties of the dyestuffs obtainable by the present process may be considerably improved by further halogenating them in the usual manner. The color of the dyestuffs is thereby not only changed to the desired kier-boiling is also enhanced.

The following examples illustrate our in- Y vention, the parts being by weight.

l. 24 parts of 4-methyl-5.6-dichloro-3-hy- ,CH; E E t t Ol- H+Ol OlglLtO \czu/ f O s N s \NH/ droxythionaphthene are dissolved in alcohol and an alkali and mixed with an alcoholic solution of 25 parts of 4-nitrosodimethylauiline. After having stirred the mass for a short time, the 4-1nethyl-5.6-dichloro-2-3-dihydro-3 -ketothionapl1thene 2- (4 d iniethylamino)-anil separates completely. It is filtered by suction and boiled for several hours together With 28 parts of 4'-b1o1no-3.2-( 3-hydroxy-1-thioph ene). naphthalene:

OH e and 400 parts of glacial acetic acid.. After pentachloride) is added. a

The dyestufi, when filtered and washed out with benzene, forms a reddish-violet powder;

it dyes cotton a violet tint of excellent fastisatin and 1000 parts of glacial acetic a id ness. I are heated to boiling. The reaction takes 3. To a solution of dibromisatin-a-chloride place according to the equation:

6. 70 parts of 4-methyl-5.6-dichlor-3-hydroxy-l-thionaphthene, 65 parts of dichlor- (obtained from 91 parts of 5.7-dibroinisatin, As soon the condensation is complete, the 200 parts of benzene and 6 parts of p p mass is allowed to cool and filtered (is by phorous pentaehloride) 1S addeda suspension ti d h lti l t fi h d of 70 P i of y until it shows a neutral reaction. It dyes droxy-l-tlnonaphthene in 10 parts 0; ben- Cotton brown tints. zencand the whole is heated for a short time 7 43 parts 0t 4 methyl 5 6 dichlorthio r e T- p to boiling. Inc d estuff, hen iilteied and napflmnegg, {aw/4616111012) mdohmhgo are washed out with benzene, dyes cotton Violet tints of excellent fastness. It has the probable (hssolvbd Whllg Coohng m 90 Parts of f l ch lorosultonic acid and gradually mined with 0 0 with 22 parts of bromine. The mixture l then stirred for half an hour in the cold and c1 poured on 500 parts of ice to which some bi sulfite solution has been added. The dyeo1\/ stufi', when filtered and washed until neutral, 5 dyes cotton violet tints of excellent fastness Br which have a bluer hue than the non-bromi- 4. To a solution of bromisatineair-chloride nated dyestuii. It has the probable formula:

(obtained from 68 parts of 5 brornisatin, 200

parts of benzene and 65 parts of phosphorous pentachloride) is added a suspension of parts of 4-methyl-5.6-dichloro-3-hydroxy-1 thionaphthene in 140 parts of benzene and C1 01 this mixture is heated for a short time to boilin g. The dyestutt, when filtered and washed s NH out with benzene, dyes cotton a violet tint of good properties as to fastness. It has the probable formula:

' Instead of the components used in the foregoing examples for the condensation with 4 methyl-5.6-dih alogen-3-hydroxythionaphthene, there may also be employed for the said purpose other diketones or derivatives thereof.

We claim: 1

5. To a solution of 59 parts of B-naphthisatin-u-chloride 200 parts of benzene, and 67 1 A new d t th t d t ff f th parts of phosphorous pentachloride is added General f 1 a suspension of 70 parts of 4-1nethyl-5.6-dib ehloro-3-hydroxy-1-thionaphthene in 140 parts of benzene and the mixture is heated to O boiling. The dyestufi', when filtered and washed out with benzene, forms a blue powmg der. It dyes cotton bright blue tints. It has L the probable formula: g 8/ l CH; O O

whereln C, represents a carbon atom belong- C1 ing to the five-membered nucleus of an isatin o1 compound and X represents hydrogen which may be replaced by halogen.

2. A new products the vat (lyestufis of the general formula:

wherein C and C represent carbon atoms belonging to an aromatic nucleus and X rep resents hydrogen which may be replaced by halogen.

3. As new products the vat dyestuffs of the general formula:

wherein the benzene nucleus R may be sub- 55 sfituted by halogen and represents hydrogen which may be replaced by halogen.

In testimony whereof, we affix our signatures.

HERMANN WAGNER. 39 I RUDOLF BRUNE. MAX HESSENLAND.

ERWIN HOFFA. FRITZ MULLER. HANS HEYN A. 

